Catalytic hydrosilylation of carbonyl compounds by hydrido thiophenolato iron(II) complexes

Article abstract of DOI:10.1016/j.catcom.2017.02.008

The hydrosilylation of aldehydes and ketones under mild conditions with hydrido thiophenolato iron(II) complexes [cis–Fe(H)(SAr)(PMe₃)₄] (1–4) as catalysts is reported using (EtO)₃SiH as an efficient reducing agent in the yields up to 95%. Among them complex 1 is the best catalyst. Complex 1 could also be used as catalyst to reduce the α,β-unsaturated carbonyl compounds selectively to the α,β-unsaturated alcohols in high yields.

Full text of DOI:10.1016/j.catcom.2017.02.008

Accepted Manuscript
Catalytic hydrosilylation of carbonyl compounds by hydrido
thiophenolato iron(II) complexes
Benjing Xue, Hongjian Sun, Qingfen Niu, Xiaoyan Li, Olaf Fuhr,
Dieter Fenske
PII:
DOI:
Reference:
S1566-7367(17)30053-5
doi: 10.1016/j.catcom.2017.02.008
CATCOM 4936
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Catalysis Communications
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Accepted date:
7 December 2016
8 February 2017
9 February 2017
Please cite this article as: Benjing Xue, Hongjian Sun, Qingfen Niu, Xiaoyan Li, Olaf
Fuhr, Dieter Fenske , Catalytic hydrosilylation of carbonyl compounds by hydrido
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ACCEPTED MANUSCRIPT
Catalytic Hydrosilylation of Carbonyl Compounds by Hydrido Thiophenolato
Iron(II) Complexes
Benjing Xuea, Hongjian Suna, Qingfen Niua,b, Xiaoyan Lia,*, Olaf Fuhrc and Dieter
Fenskec
aSchool of Chemistry and Chemical Engineering, Key Laboratory of Special
Functional Aggregated Materials, Ministry of Education, Shandong University,
Shanda Nanlu 27, 250199 Jinan, PR China
bShandong Provincial Key Laboratory of Fine Chemicals, Qilu University of
Technology, Jinan 250353, PR China
cInstitut für Nanotechnologie (INT) und Karlsruher Nano-Micro-Facility (KNMF),
Karlsruher Institut für Technologie (KIT), Hermann-von-Helmholtz-Platz 1, 76344
Eggenstein-Leopoldshafen, Germany
E-mail: xli63@sdu.edu.cn; Fax: + 86 531 88564464.
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Abstract: The hydrosilylation of aldehydes and ketones under mild conditions with
hydrido thiophenolato iron(II) complexes [cis–Fe(H)(SAr)(PMe3)4] (1 - 4) as catalysts
is reported using (EtO)3SiH as an efficient reducing agent in the yields up to 95%.
Among them complex 1 is the best catalyst. Complex 1 could also be used as catalyst
to reduce the α,β-unsaturated carbonyl compounds selectively to the α,β-unsaturated
alcohols in high yields.
Keywords: hydrosilylation / silane / iron hydride /α,β-unsaturated carbonyl
compound / carbonyl compound
2

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1. Introduction
Transition-metal-catalyzed hydrosilylation of carbonyl derivatives is an exceedingly
attractive and convenient reduction method because it generates silyl protected
alcohols in one step under mild conditions [1 - 4]. Hydrosilylation of unsaturated
organic substrates containing C=C, C≡C, C≡N, and C=O bonds is an important
industrial and laboratory reaction widely used for preparation of useful organosilicon
monomers and polymers, crafting of surfaces, as well as production of special silicon
chemicals [5 - 10]. Thus, transition-metal-catalyzed hydrosilylation is recognized as a
powerful and indispensable tool in organic synthesis, because both the reduction and
the protection steps are performed in a single, atom-efficient fashion.
Due to the high abundance, low cost and environmental friendliness of iron, iron
compounds as catalysts have attracted more and more attention in the field of
synthetic chemistry. Recently, Bauer and Knölker summarized iron-catalyzed organic
reactions in organic synthesis [11] as a representative pioneering example, Brunner et
al. reported the hydrosilylation of acetophenone with Fe(Cp)(CO) complex as catalyst
under photo-irradiation [12, 13]. Chirik and co-workers studied complexes
[Fe(iPrPDI)(CH2TMS)2] as catalysts for the hydrosilylation of ketones at room
temperature achieving a good activity [14]. Beller described that simple complex
Fe(OAc)2 in the presence of phosphine ligands could be an active catalyst in the
reductions of aldehydes and ketones with broad substrate scope and high tolerance
against several functional groups [15]. Similarly, Nishiyama and co-workers also
chose Fe(OAc)2 but with nitrogen ligand as catalyst to be used in hydrosilylation of
ketones to give the corresponding alcohols in high yields [16]. Simple amide catalyst
[Fe(N(SiMe3)2)2] could also catalyze hydrosilylation of carbonyl compounds at room
temperature [17]. Although considerable progress has been made in iron-catalyzed
hydrosilylations, up to date, there are only a few studies published on iron hydride
complexes as pre-catalysts for hydrosilylation of carbonyl derivatives [18 - 21]. In
2008, Nikonov reported iron silyl dihydride displaying a good catalytic property in
the hydrosilylation of carbonyls [18]. In 2011, Guan and co-workers described a
family
of
well-defined
iron
POCOP-pincer
hydrido
complexes
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[2,6-(R2PO)2C6H3]Fe(H)(PMe3)2, [2,6-(i-Pr2PO)2C6H3]Fe(H)(PMe3)(CO)n (n = 1, 2),
which were active catalysts for the hydrosilylation of aldehydes and ketones with
different functional groups [19]. Darcel reported the iron dihydrido complex
[(dppe)2Fe(H)2] as the pre-catalyst for efficient hydrosilylation of carbonyl derivatives
under visible light activation [20]. Most recently, some pincer-type iron complexes
[22, 23], bidentate iron complexes [24, 25] and dinuclear iron complexes [26, 27]
were reported as catalysts for the reduction of carbonyl compounds. Our group
reported the synthesis of several pincer iron(II) hydrides and bidentate iron(II)
hydrides which can be used as catalysts in the hydrosilylation of aldehydes and
ketones (Fig. 1) [13, 28 - 32]. We have reported the synthesis of hydrido
thiophenolato iron(II) complexes 1 - 4 by reaction of thiophenols with Fe(PMe3)4 (Fig.
2). Complexes 1 – 4 could be used as catalysts in the reduction of primary amides to
nitriles under hydrosilation conditions [33, 34]. As continuation to our study in this
direction, in this paper we reported the reduction of carbonyl derivatives under
hydrosilylation condition in the presence of hydrido iron(II) complexes 1 – 4.
Complexes 1 – 4 showed excellent catalytic activity in the hydrosilylation of
aldehydes and ketones using (EtO)3SiH as a reducing agent under mild conditions in
excellent yields with a broad functional group tolerance.
PMe3
H
Fe
Ph2
P
PPh
PPh2
PMe3
2
O
O
P
Me3P
PMe
Ph2
But
tBu
3
3
Me Si Fe
H
Fe
PMe
H
PMe3
PPh
PPh2
2
tBu
tBu
Me3P
H
PMe3
H
Me3P
H
PMe3
Fe
N
F
H
Me3P
Ph
P
2
Fe
N
F
H
Me3P
PMe
PMe
3
Fe
F
F
3
F
S
PMe
F
3
Fig. 1 Hydrido iron(II) precatalysts for hydrosilylation by our group
Furthermore, we have explored the selectivity of complex 1 as catalyst in the
reduction of α,β-unsaturated carbonyl compounds to the corresponding alcohols in
high yields.
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PMe3
Fe
PMe3
Fe
H
H
PMe3
PMe3
PMe3
PMe3
S
S
PMe3
PMe3
TMS
1
2
Me
PMe3
Fe
PMe3
Fe
H
S
H
PMe3
PMe3
PMe3
PMe3
MeO
S
PMe3
PMe3
4
3
Fig. 2 Thiophenolato hydrido iron(II) complexes 1 - 4
2. Experimental section
General procedures and materials. Standard vacuum techniques were used in the
manipulations of volatile and air-sensitive materials. Solvents were dried by known
procedures and distilled under nitrogen before use. Infrared spectra (4000 − 400 cm−1),
as obtained from Nujol mulls between KBr disks, were recorded on a Bruker ALPHA
FT-IR instrument. NMR spectra were recorded using Bruker Avance 300 MHz
spectrometers. GC-MS was recorded on a TRACE-DSQ instrument and GC was
recorded on a Fuli 9790 instrument. All the aldehydes, ketones and α, β-unsaturated
carbonyl compounds were purchased and used without further purification. The purity
of the triethoxysialne used is 95%, the other 5% is tetraethoxysialne. The silanes were
purchased from J&K scientific. Fe(PMe3)4 [35] and complexes 1 – 4 [33, 34] were
prepared according to literature procedures.
Caution! (EtO)3SiH is flammable and highly toxic by inhalation and may cause skin
irritation and blindness. Even if during our studies on the hydrosilylation of carbonyl
compounds, we used it without incident, triethoxysilane should be used with
precaution. Indeed, due to possible silane disproportionation, the formation of an
extremely pyrophoric gas (possibly SiH4) has led to several fires and explosions
reported in the literature. (See Buchwald safety letter, Chemical & Engineering News
(29 Mar 1993) Vol. 71, No. 13, pp. 2.)
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General Procedure for Catalytic Hydrosilylation of Aldehydes. To a 25 mL
Schlenk tube containing a solution of 1 in 2 mL of THF was added an aldehyde (1.0
mmol) and (EtO)3SiH (0.20 g, 1.2 mmol). The reaction mixture was stirred at 50 -
55°C until there was no aldehyde left (monitored by TLC and GC-MS). The reaction
was then quenched by MeOH (2 mL) and a 10% aqueous solution of NaOH (5 mL)
with vigorous stirring at 60°C for about 24h. The organic product was extracted with
diethyl ether (10 mL × 3), dried over anhydrous MgSO4, and concentrated under
vacuum. The alcohol product was further purified using flash column chromatography
1
(elute with 5 - 10% ethyl acetate in petroleum ether). The H NMR and 13C NMR
spectra of the alcohol products are provided in the Supporting Information.
General Procedure for the Catalytic Hydrosilylation of Ketones. Ketones were
reduced following a similar procedure to the one used for aldehydes except that the
1
reaction time of heat was extended to 24h and the temperature rised to 60°C. The H
NMR and 13C NMR spectra of the alcohol products are provided in the Supporting
Information.
General Procedure for the Catalytic Hydrosilylation of α,β-unsaturated carbonyl
compounds. α,β-unsaturated carbonyl compounds were reduced following a similar
1
procedure to the one used for aldehydes. The H NMR and 13C NMR spectra of the
corresponding alcohol products are provided in the Supporting Information.
3. Results and discussion
3.1. Catalytic application of iron hydrido complexes 1 - 4 in hydrosilylation of
aldehydes and ketones
As mentioned previously, transition-metal catalysts can effectively reduce a wide
variety of unsaturated organic substrates. Our group have recently reported the
hydrosilylation of carbonyls catalyzed by different iron(II) hydrides[13, 25-29]. In
comparison with the above-mentioned hydrides, as monodentate hydrido complexes,
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1 - 4 as catalysts have more advantages. For example, the synthesis of complexes 1 - 4
is easier and they are more inexpensive. Therefore, to extend the scope of the
iron-based catalyst, the catalytic property of complexes 1 - 4 was further studied.
1) 1 1mol%, THF
(1)
PhCH2OH
PhCHO + (EtO)3SiH
2) 10% NaOH, MeOH
Table 1 Exploration of Reduction of Benzaldehyde Catalyzed by 1 - 4a
Entry Complex
Loading
Hydrogen
source
Solvent
Temp.
Time
(h)
2
bConv.
(%)
0
(℃)
(mol%)
0
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
(EtO)3SiH THF
(EtO)3SiH THF
(EtO)3SiH THF
(EtO)3SiH THF
(EtO)3SiH THF
(EtO)3SiH THF
50
50
50
50
50
50
50
50
50
50
50
50
50
15
30
60
50
50
50
2
0.5
1
2
67
99
29
57
83
0
3
2
4
1
0.5
1.0
1.5
2
5
1
6
1
7
1
Et3SiH
Ph3SiH
THF
THF
8
1
2
0
9
1
Me2PhSiH THF
2
31
59
87
43
0
10
11
12
13
14
15
16
17
18
19
20
1
Ph2SiH2
PhSiH3
TMDS
PMHS
THF
THF
THF
THF
2
1
2
1
2
1
2
1
(EtO)3SiH THF
(EtO)3SiH THF
(EtO)3SiH THF
(EtO)3SiH Toluene
(EtO)3SiH Ether
(EtO)3SiH Pentane
2
49
83
88
57
51
26
43
1
2
1
2
1
2
1
2
1
2
1
(EtO)3SiH Isopropanol 50
2
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21
22
23
24
25
26
2
2
3
3
4
4
1
1
1
1
1
1
(EtO)3SiH THF
(EtO)3SiH THF
(EtO)3SiH THF
(EtO)3SiH THF
(EtO)3SiH THF
(EtO)3SiH THF
50
50
50
50
50
50
2
6
2
3
2
4
47
99
79
99
65
99
a
Catalytic reaction conditions: PhCHO (1.0 mmol), (EtO)3SiH (1.2 mmol),
n-dodecane (internal standard) (1.0 mmol), 1 - 4 (0.01 mmol) in 2 ml THF, T℃, t h.
b Determined by GC analysis.
The hydrosilylation of aldehydes using (EtO)3SiH as the reducing silylating agent was
studied with thiophenolato hydrido iron(II) complexes 1 – 4 as catalysts (Eq. (1),
Table 1). To explore the activity of complexes 1 - 4 in hydrosilylation, benzaldehyde
was chosen as the model substrate by using (EtO)3SiH as a hydrogen source in THF at
50℃. The reaction didn’t proceed without any catalyst (entry 1, Table 1). To our
delight, in the presence of 1 mol% of 1, the reaction was completely finished within
2h (entry 2, Table 1). However, at the given conditions, complexes 2 - 4 seemed to be
less active than 1 (entries 21 - 26, Table 1). The conversion was lower when reaction
time was shorter than 2h (entries 4 - 6, Table 1). ). When (EtO)3SiH was replaced by
other silanes, such as Et3SiH, Ph3SiH, Me2PhSiH, Ph2SiH2, PhSiH3, TMDS or PMHS,
the results were unsatisfactory (entries 7 - 13, Table 1). Temperature and solvent were
two factors in this hydrosilylation reaction. The conversion was not good at the
temperature below or above 50℃ (entries 14 - 16, Table 1). The conversion in polar
solvent (THF) (entry 3, Table 1) was better than those in the other four solvents
(entries 17 - 20, Table 1). The optimized catalytic reaction conditions can be
summarized as follows: PhCHO (1.0 mmol), (EtO)3SiH (1.2mmol), and 1 (0.01 mmol)
in 2.0 ml of THF, 50℃, 2h.
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1) 1 1mol%, THF
(2)
RCHO + (EtO)3SiH
RCH2OH
2) 10% NaOH, MeOH
After optimization of the catalytic reaction conditions, more substrates of aldehydes
bearing different functional groups were selected to explore the scope of this catalytic
system (Eq. (2), Table 2). After workup, the corresponding alcohols were settled in
high yields (Table 2). It could be concluded that the substrates substituted by halogen
(either mono-substituted or bis-substituted) converted to corresponding alcohols in
good yields under the mild conditions. The substrates with electron-donating group
(Me, MeO) gave moderate yields (83% and 80% respectively). In addition,
heterocyclic compounds furaldehyde and thiophenecarboxaldehyde also reacted well
and the yields were very high (92%, 95%). Aliphatic aldehyde like
phenylacetaldehyde and n-butanal performed in good yields (73% and 87%). The
aldehydes bearing different functional groups such as nitro, ester, nitrile, tertiary
amides, secondary amides and ester could also be reduced to the corresponding
alcohols in high yields (91%, 83%, 81%, 77%, 71% and 89% respectively).
Table 2 Catalytic Hydrosilylation of Aldehydes with 1 as Catalyst.a,b
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Cl
Br
F
CH2OH
CH2OH
CH2OH
CH2OH
84%
93%
86%
92%
CH2OH
CH2OH
CH2OH
Cl
Br
F
88%
93%
90%
CH2OH
CH2OH
CH2OH
Cl
Cl
MeO
80%
94%
91%
73%
Cl
CH2OH
CH2OH
S
CH2OH
CH2OH
F
Br
Me
Cl
O
83%
95%
90%
CH2OH
CH2OH
OH
87%c
92%
85%
NO2
OAc
CH2OH
CH2OH
CH2OH
NC
81%
91%
83%
CH2OH
CH2OH
CH2OH
Me2N
H3CO
MeHN
O
O
O
71%
77%
89%
a
Catalytic reaction conditions: (1) RCHO (1.0 mmol), (EtO)3SiH (1.2 mmol) and 1
(0.01 mmol) in 2 ml THF, 50℃, 2h. (2) MeOH (2 mL) and 10% aqueous solution of
NaOH (5 mL) with vigorous stirring at 60°C for about 24h.
b Isolated Yield.
c GC Yield.
O
OH
H
1) 1 2 mol%, THF
+ (EtO)3SiH
(3)
2) 10% NaOH, MeOH
R
R'
R
R'
For ketones, these hydrosilylation reactions were obviously sluggish during the
required reaction time and their yields were lower within 2 h. Therefore, increasing
the catalyst loading to 2%, extending reaction time to 24h and raising the temperature
seemed to be useful for the reaction (Eq. (3), Table 3). This result might be attributed
10

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to the steric hindrance in the reaction. So in the catalytic exploration of ketones, the
reaction process seems difficult.
Table 3 Catalytic Hydrosilylation of Ketones with 1 as Catalyst.a,b
OH
OH
OH
F
MeO
73%
82%
70%
OH
OH
OH
Cl
89%
79%
77%
OH
OH
OH
N
87%c
69%
70%
a
Catalytic reaction conditions: (1) RCOR’ (1.0 mmol), (EtO)3SiH (1.2 mmol) and 1
(0.02 mmol) in 2 ml THF, 60℃, 24h. (2) MeOH (2 mL) and 10% aqueous solution
of NaOH (5 mL) with vigorous stirring at 60°C for about 24h.
b Isolated Yield.
c GC Yield.
3.2. Selective reduction of α,β-unsaturated carbonyls catalyzed by complex 1.
Using complexes 1 as catalysts, we have further explored the reduction of
cinnamaldehydes. It was found that the cinnamaldehydes were selectively reduced to
the corresponding cinnamyl alcohols in good yields under mild conditions. This
selectivity is similar with our early reported system [28, 29]. Several substrates were
studied in order to explore the scope of this catalytic system (Eq. (4), Table 4).
Cinnamyl alcohols could be obtained from corresponding cinnamaldehydes whatever
the substituent group was. It’s worth noting that the α-Me substitutional cinnamyl
alcohol was obtained in the highest yield. We think that the methyl, as an
electron-donating group, increased the electron density at the oxygen atom. This
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makes the O atom easier to coordinate to central iron atom, thus, the yield was
enhanced. In the case of α-bromocinnamaldehyde, 3-phenyl-2-propyn-1-ol was
isolated in the yield of 75 %, this is produced by the elimination of HBr from the
corresponding cinnamyl alcohol [28]. ,-Unsaturated ketones are also applicable to
this catalytic system by increasing the catalyst loading to 2%, extending reaction time
to 24h and raising the temperature to 60°C (Table 4).
OH
O
1) 1 1 mol%,
H
H
THF
(4)
R1
(EtO)3SiH
R1
2) 10% NaOH,
MeOH
R2
R2
Table 4 Selective reduction of α,β-unsaturated carbonyls catalyzed by 1.a,b
OH
OH
OH
H
H
88%
91%
75%
OH
OH
H
H
(
)
5
Cl
70%
78%
OH
79%
a Catalytic reaction conditions: (1) cinnamaldehyde (1.0 mmol), (EtO)3SiH (1.2 mmol)
and 1 (0.01 mmol) in 2 ml THF, 50℃, 4h. (2) MeOH (2 mL) and 10% aqueous
solution of NaOH (5 mL) with vigorous stirring at 60°C for about 24h.
b Isolated Yield.
In comparison with our early reported systems, we can find that, as monodentate
hydrido complexes, 1 - 4 as catalysts have almost the similar activity as the pincer
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iron(II) hydrides [13, 26, 27] and bidentate iron(II) hydrides [25, 28, 29] in the
hydrosilylation of aldehydes and ketones. In most cases, the catalytic activity of
complexes 1-4 are more higher than that of the related bidentate iron(II) hydrides with
[P, S]-cheating ligand, especially in the hydrosilylation of ketones [29].
4. Conclusions
In conclusion, hydrido thiophenolato iron(II) complexes [cis–Fe(H)(SAr)(PMe3)4] (1 -
4) could be used as catalysts for the hydrosilylation of carbonyl compounds. Among
them complex 1 is the best catalyst. Furthermore, α,β-unsaturated alcohols could be
obtained from the selective reduction reactions of the corresponding α,β-unsaturated
carbonyls catalyzed by hydrido iron(II) complex 1. We have compared the efficiency
of our catalyst (1 mol%, 50 °C, 2 h for aldehydes and 2 mol%, 60 °C 24 h for ketones)
with Chirik’s [14], Nikonov’s [18] and Tilley’s [17] results. In general, catalyst
efficiency of Chirik’s catalytic system (0.1% - 1 mol% catalyst loadings and at 23°C)
is better than that of our catalytic system. Although the catalyst loadings (5 mol% and
2.7 mol%) of Nikonov’s and Tilley’s system are larger than that of our system (1
mol% and 2 mol%), even if the reaction temperatures (22 and 23 °C) and times (3 and
0.3 h) are more advantageous.
Acknowledgements
We gratefully acknowledge the support by NSF China No. 21372143.
Supplementary material: Electronic Supplementary Information (ESI) available: 1H
NMR and 13C NMRspectra for the alcohol products.
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ACCEPTED MANUSCRIPT
Graphical abstract
PMe
3
H
PMe
3
Fe
1)
1 - 2 mol%, THF
OH
H
PMe
O
ArS
3
PMe
3
(EtO) SH
+
3
2) 10% NaOH, MeOH
R
R'
R
R'
38 examples, yields: 69 - 95%
16

ACCEPTED MANUSCRIPT
Highlights
 Hydrosilylation of aldehyde and ketone was catalyzed by iron(II) hydride.
 Reduction of aldehyde and ketone was studied with (EtO)3SiH as reducing agent.
 α,β-Unsaturated carbonyl compound was reduced to α,β-unsaturated alcohols.
17